EP0582592A4 - Polymeric material and clear film produced therefrom. - Google Patents
Polymeric material and clear film produced therefrom.Info
- Publication number
- EP0582592A4 EP0582592A4 EP92908842A EP92908842A EP0582592A4 EP 0582592 A4 EP0582592 A4 EP 0582592A4 EP 92908842 A EP92908842 A EP 92908842A EP 92908842 A EP92908842 A EP 92908842A EP 0582592 A4 EP0582592 A4 EP 0582592A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- hmw
- films
- hdpe
- polymer
- haze
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention is directed to improvements in high density, and particularly, high density, high molecular weight polyethylene polymers, the use of such improved polymers in film and bag applications, and to a method of producing such improved polymers.
- High density polyethylene (HDPE) polymers have traditionally not been employed in the production of thin plastic films, plastic bags, and the like, which require high clarity, because these materials do not possess the requisite degree of clarity most commonly desired for many thin plastic film uses.
- clear (or semi-clear) plastic (i.e., polymeric) films or bags are formed, they are usually formed from low density polyethylene (LDPE) or mixtures of low density polyethylene polymers.
- LDPE low density polyethylene
- Conventional HDPE films and/or bags unlike LDPE films and/or bags have little or no gloss in their overall appearance, often making them undesirable to wholesale and retail consumers alike.
- the following companies produce the bulk of HDPE; Phillips 66, Exxon/Paxon, Occidental Chemical, Quantum Chemical, Solvay Polymers, Chevron Chemical, Union Carbide, Dow Chemical, and Hoechst
- LDPE films and bags produced therefrom are typically very clingy, thus making the bags hard to open.
- LDPE films and bags produced therefrom are not as strong as HDPE films and bags at an equivalent thickness.
- LDPE films are more flexible than HDPE films, which can make LDPE more difficult to run through machinery. The higher stiffness of HDPE films is one very desirable characteristic of this type of product, but the lack of high gloss and clarity has limited its applications.
- the present invention represents a dramatic breakthrough in the use of high density polyethylene polymers for the formation of clear, strong thin films and bags.
- the present invention affords a high density polyethylene material which can be formed into a thin film having many of the desirable qualities of both high and low density polyethylene materials, without the disadvantages associated with either class of material.
- the film and/or bags produced therefrom are stronger at an equivalent thickness, have the requisite high clarity, and have less cling than those films and/or bags formed from traditional low density polyethylene polymers. Since the polymer of the present invention is a high density polyethylene, less polymer is required to form a film or bag having superior strength characteristics in comparison to the traditional low density polymers. In addition, since the polymer of the present invention is a high molecular weight, high density material, it yields a ⁇ tiffer film and/or bag at comparable thicknesses to a conventional LDPE polymer, which makes the processing of- the film through machinery better, and extends the applications of the material beyond that traditionally envisioned for LDPE films and/or bags.
- U.S. Patent No. 2,983,704 (Roedel) describes a film of polyethylene comprising a solid ethylene polymer having a density of 0.9137 at 25°C, and from 10 to - _ -
- U.S. Patent No. 1,234,567 (Tritsch) describes a pressure-sensitive adhesive tape having a molecularly oriented polyethylene film backing and a pressure- sensitive adhesive mass on at least one side thereof, said backing comprising a blend of high density polyethylene having a density of from about 0.95 to about 0.98 and low density polyethylene having a density of about 0.92 wherein said high density polyethylene is present in an amount from about 5% to less than about 20 percent of the blend.
- U.S. Patent No. 3,125,548 (Anderson) describes a polyethylene blend comprising 20 to 45 weight percent of a polyethylene having a density of less than 0.920 g/cc, 30 to 60 weight percent of a polyethylene resin having a density of 0.1924 to 0.933 g/cc and at least 10 weight percent of a polyethylene resin having a density above 0.945 g/cc.
- U.S. Patent No. 3,176,051 (Gregorian et al . ) describes a blended composition, comprising polyethylene having a density in the range 0.94 to 0.97 and a melt index in the range 0.5 to 10 and a minor amount, i.e., between 0.1 to 10% by weight of said composition of an additive member of the group consisting of polyethylene having a reduced viscosity in the range 2.9 to 10 and a copolymer of ethylene and
- U.S. Patent No. 3,340,328 (Brindell et al.) describes a homogeneous, polyethylene composition comprising a blend of (a) from 15 percent to 25 percent by weight of a straight chain polyethylene characterized as having a density of from 0.95 g/cc, to 0.96 g/cc, at 23°C, and in having a melt index in the range of 3 to 15 g/10 minutes through a 2.1 mm orifice at 190°C, and under a 2.16 kg weight; and (b) from 85 percent to 75 percent of a linear polyethylene having an average molecular weight exceeding 750,000 and characterized as having a density of between approximately 0.925 g/cc, and 0.935 g/cc, at 23°C, a melt index of about 0.30 g/10 minutes at 250°c, and 2,740 p.s.i., and an initial melting point of between
- U.S. Patent No. 3,231,636 (Snyder) describes a composition possessing improved shear strength and resistance to thermal embrittlement comprising 50 to 8: parts by weight of a polyethylene resin having a specific gravity above 0.945 and a melt index between about 0.02 and 8.0 and 50 to 15 parts by weight of a polyethylene resin having a specific gravity between about 0.915 and 0.925 and a melt index between about 0.02 to 25.0.
- U.S. Patent No. 3,375,303 describes a composition comprising low density polyethylene having a density of from about 0.915 to about 0.925 and from about 1 to about 9 percent by weight, based on the weight of the composition of high density, high molecular weight polyethylene of narrow molecular weight distribution having a density of from about 0.930 to about 0.965, a melt index of not more than 0.: decigrams per minute measured at 44 p.s.i. and 190°C, and a melt flow of not more than 10 decigrams per minute measured at 440 p.s.i. and 190°C, the melt index of said low density polyethylene being no greater than about 30 times the melt index of the high density polyethylene.
- U.S. Patent No. 3,381,060 (Peacock) describes a composition exhibiting freedom from melt fracture comprising low density polyethylene having a density of from about 0.915 to about 0.925, from about 0.3 to about 8 percent by weight of a first high density polyethylene having a density of from about 0.930 to about 0.965, a melt index of not more than 0.1 decigram per minute measured at 44 p.s.i. and 190°C, and a melt flow of not more than 10 decigrams per minute measured at 440 p.s.i.
- melt index of said low density polyethylene being no greater than about 250 times the melt index of said first high density polyethylene.
- melt flow disturbances can be reduced by selecting resins that contain relatively low concentrations of large molecules and by intense mechanical deformation of the melt before extrusion. Melt index swell decreased with number of extrusions and correlated well with degree of haze reduction.
- extensional flow tests were the most sensitive, but other sensitive rheological tests included those that were dominated by long time constants. This includes the complex modulus.
- the present invention is directed to a high molecular weight, high density polyethylene (HMW-HDPE) polymer which can be formed into a thin film having many of the desirable qualities of both high and low density polyethylene materials, without the disadvantages commonly associated with eirher class of material.
- HMW-HDPE high density polyethylene
- the HMW-HDPE polymer of the present invention has a molecular weight range of about 450,000 to 650,000, a density range of from about 0.941 to 0.950, and a melt index of about 0.5 g/10 min.
- Thin films produced from this composition have the following physical properties:
- Low haze i.e., high clarity
- the percentage of haze in the films of the present invention is less than about 50 percent, preferably less than about 35 percent, and most preferably less than about 20 percent, as measured by ASTM D-1003.
- Conventional HDPE polymer based films have haze values typically in excess of 50, 60 and/or 70 percent when measured in this manner. (See Table I and II, infra) .
- High Gloss (45°) are at least about 20, preferably at least about 30 and most preferably at least about 40, as measured by ASTM D-2457.
- Conventional HDPE polymer based films have gloss values typically below about 15 and/or 10 when measured in this manner. (See Table I and II, infra) .
- the percentage of light transmission for the films of the present invention are at least about 85 percent, preferably at least about 90 percent, as measured by ASTM D-1003.
- Conventional HDPE polymer based films have similar high light transmission percentages.
- the HDPE polymer of the present invention retains this favorable characteristic. (See Table I and II, infra) .
- the films of the present invention show variation in moisture vapor transmission (MVTR) values when compared to conventional HMW-HDPE polymer films as measured using ASTM F-372. In some cases the MVTR values increased from about 3 to 20 percent; while in other cases MVTR values decreased up to about 10 percent. (See Table
- the films of the present invention show an increase in N 2 gas permeation values when compared to conventional HMW-HDPE polymer films ranging from about 1.5% up to about 17.2% as measured using ASTM D-3985. (See Table I and II, infra) .
- the films of the present invention show an increase in 0 2 gas permeation values when compared to conventional HMW-HDPE polymer films ranging from about 3% up to about 22% as measured using ASTM D-3985. (see Table I and II, infra) .
- thin films is defined as a film having a thickness of less than 1.5 Mil, preferably less than 1.0 Mil, and most preferably less than 0.75 Mil.
- HMW-HDPE high molecular weight, high density polyethylene
- HMW-LDPE high molecular weight low density polyethylene
- the resulting polymer formed by the above described blending and extrusion is not merely a mixture of the individual ingredients. It is believed that during the extrusion process, the crystalline structure of the two individual polymers is modified, resulting in the formation of a new polymer. Such change is believed due to the action of the heat and pressure of the extruder.
- This new polymer affords films and/or bags exhibiting high strength, high clarity, high gloss, low haze, and high slip.
- the film and/or bags prepared from this new polymer have exceptional strength, high gloss or sheen, and better transparency than conventional HMW-HDPE film based bags.
- this invention is also directed to a method of improving the haze properties of clear films prepared from high molecular weight high density polyethylene resins, which method comprises adding a haze reducing amount of a high molecular weight low density polyethylene resin to said HMW-HDPE resins and forming films from the blended resin mixture.
- one of the most preferred formulations of the aforementioned blend of a HMW-HDPE resin and a LDPE resin in this invention is 80% (by weight) of Novacor's Novapol HD-4045 and 20% (by weight) of Quantum USI's Petrothene NA 355.
- the ranges of these materials which can be effectively used to make the film and/or bags of the present invention are as follows:
- a second preferred polymer blend formulation which has been developed herein is 79% Novacor's Novapol HD-4045, 20% USI's Petrothene NA 355 and 1% Archer Daniels Midland's Polyclean II 20835. It should be noted that USI's Petrothene NA351 can be substituted for the NA 355. Also, USI's Petrothene NA357 is another acceptable material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
- the present invention is directed to improvements in high density polyethylene (HDPE) polymers, the use of such improved polymers in film and bag applications, and to a method of producing such improved polymers.
- HDPE high density polyethylene
- the present invention is directed to a novel polymeric material and most particularly to films and/or thin, strong, high clarity bags, (e.g., produce and bakery bags) produced from this polymeric material.
- Table II provides additional physical data for some he polymeric formulations described in Table I.
- the new polymeric material may be formed during the compounding, in the other, it is clearly formed in situ (i.e., in the extruder).
- While one route used to prepare the novel polymeric composition of the present invention is based upon the physical blending of two (or more) materials together, followed by extrusion of the blend to produce the novel polymeric product, it is envisioned other processes may be employed.
- those artisans having ordinary skill in the polymer art will be able to prepare the same polymeric product, having the described desired properties, using a variety of different techniques, e.g., in a polymer reactor vessel.
- the present inventors anticipate that artisans having ordinary skill in this field will be able to avoid the blending step described above, and still produce the presently claimed polymeric composition.
- the novel polymer of the present invention has exceptional properties, which allows its use in numerous film and/or bag applications, including:
- a substrate film for metallization and high moisture, light and air barrier food bags prepared therefrom e.g., coffee, snack foods, such as candy, chips, peanuts, etc.
- a substrate film for metallization and high moisture, light and air barrier food bags prepared therefrom e.g., coffee, snack foods, such as candy, chips, peanuts, etc.
- a substrate film for metallization and high moisture, light and air barrier food bags prepared therefrom e.g., coffee, snack foods, such as candy, chips, peanuts, etc.
- (h) as a heat stable film material e.g., to be used to cover food for microwave warming, heating and cooking.
- the mixture of HMW-HDPE (e.g., Novapol's HD-4045) and the HMW-LDPE (e.g., Quantum's NA 355) can be run through a commercial blown film extruder to produce films ranging in thickness from about 0.000275 inches to about 0.0005 inches.
- Quantum's NA 355, one of the preferred resins used herein includes the following guidelines for its use:
- a long-stalk bubble shape is recommended if HMW-LDPE films under 1.5 mil are being extruded.
- the extrudate above the die is kept at the same diameter as the die until the bubble expands to its final diameter just below the frost line, the point where the molten resin solidifies.
- the long stalk is maintained by a single-lip air ring around the die.
- Quantum's HMW-LDPE resins can be drawn down to 0.5 mil and retain their high strength and clarity properties, provided they are extruded using the long-stalk technique.
- Table III lists other properties of Quantum's HMW-LDPE resins for film when blown under long-stalk conditions.
- Novapol HD-4045 is a high molecular weight, high density film resin for thin gauge, high-strength film applications. This material is advertized by its manufacturer as being designed to be drawn as low as 13 microns (0.5 mil). HD-4045-H offers the film processor high output rates for demanding film applications such as merchandise bags, T-shirt bags, can liners, mailing envelopes and other paper replacement end-uses.
- HD-4045-H is said to process well on blown film lines designed for high density polyethylene extrusion, as well as on low shear, low L/D grooved barrel extruders. Film produced from this resin can readily be treated, printed and heat sealed on a variety of converting equipment.
- Table IV outlines physical properties of HD-4045-H of importance in the present invention.
- HMW-HDPE high molecular weight high molecular weight high density polyethylenes
- Petrothene R ' high density polyethylene resins for blown and cast films (U.S. Industrial Chemicals Co.,) such as LY 600.
- High density polyethylene HD-7000F blown film resin (Exxon Chemical Co.)
- Alathon( R ) L5005 HDPE resin a high molecular weight HDPE resin (Cain Chemical Inc.) whose broad bimodal molecular weight distribution (MWD) can be controlled by production technology.
- HMW HDPE resins While a number of HMW HDPE resins have been described, it is similarly believed that the skilled artisan will readily see that NA 355 is not the only HMW-LDPE resin which can be used to improve the gloss and haze values of films and bags prepared from HMW-HDPE resins. Upon consideration of the present disclosure, the skilled artisan will readily be capable of determining substitute, equivalent, and/or superior materials for formulating polymers, films and/or bags having the unique properties described herein.
- DSC crystallinity measurements of several films prepared according to the present invention reveal that film clarity and haze are not related to rhe degree of crystallinity of the final film.
- Polymer crystal size is also not related to film clarity and haze, as demonstrated by polarized light microscopy and interference microscopy of icrotomed cross sections of film.
- the Novapol HD-4045 and Petrothene NA 355 are blended together in a 4:1 ratio (i.e., 80% - 20%) respectively.
- the blend is then run through a blown film extruder at a 4:1 blow-up ratio and produces a 8"
- Example 1 is repeated, but the formulation comprises 79% Novacor's Novapol HD-4045, 20% USI's Petrothene NA 355 and 1% Archer Daniels Midland's Polyclean II 20835.
- Example 1 is repeated, but USI's Petrothene NA 351 is substituted for the NA 355.
- Example 1 is repeated, but USI's Petrothene NA 357 is substituted for the NA 355.
- Test Geometry Parallel Plate - 25 mm diameter, with a typical gap height of 1 to 2 mm.
- Test Frequencies 0.1 to 100 rad/sec; 5 points per decade Strain Level: 25%
- test specimens 1 to 1.5 grams of each polymeric material were used for each experiment. Test specimens were loaded at temperatures ranging from 25°C to 70°C. After loading, the temperature was raised in order to melt the specimen. Initially, the specimens underwent thermal expansion and exerted an outward normal force on the parallel plates. Therefore, the gap setting had to be adjusted periodically to avoid a normal force overload to the instrument.
- test specimens began to melt, and the normal forces decreased.
- the test material was then compressed between the parallel plates until it clearly filled the entire gap. Next, the excess material was trimmed from the edge of the plates. Finally, the test specimen was compressed again, with the operator making sure that the entire gap was filled with polymer melt. Once the temperature of the specimen reached the desired level, the specimen was allowed to equilibrate for 5 minutes before testing was begun.
- the materials did not exert an excessive torque at the highest test frequency (100 rad/sec) . 2. The materials did exert a sufficient torque at the lowest test frequency (0.1 rad/sec)
- the overall degree of reproducibility was from 2 to 3%. This is considered good.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US67753491A | 1991-03-29 | 1991-03-29 | |
US677534 | 2000-10-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0582592A1 EP0582592A1 (en) | 1994-02-16 |
EP0582592A4 true EP0582592A4 (en) | 1995-02-22 |
Family
ID=24719100
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92908842A Withdrawn EP0582592A4 (en) | 1991-03-29 | 1992-03-27 | Polymeric material and clear film produced therefrom. |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0582592A4 (en) |
JP (1) | JPH06506245A (en) |
AU (1) | AU1573492A (en) |
BR (1) | BR9205821A (en) |
CA (1) | CA2107095A1 (en) |
WO (1) | WO1992017539A1 (en) |
ZA (1) | ZA922301B (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2278363B (en) * | 1993-05-28 | 1996-10-30 | Chaloke Pungtrakul | A method for the prevention of blocking in linear low density polyethylene films |
USRE38429E1 (en) * | 1996-03-12 | 2004-02-17 | Tyco Plastics Services Ag | Stretch wrap films |
US5976682A (en) * | 1996-03-12 | 1999-11-02 | Tenneco Packaging | Stretch wrap films |
US5998017A (en) * | 1996-03-12 | 1999-12-07 | Tenneco Packaging | Stretch wrap films |
US5902684A (en) * | 1996-03-12 | 1999-05-11 | Tenneco Packaging Inc. | Multilayered Metallocene stretch wrap films |
US5989725A (en) * | 1997-01-16 | 1999-11-23 | Tenneco Packaging | Clear high molecular weight film |
FR2760823B1 (en) * | 1997-03-11 | 1999-04-23 | Air Liquide Sante Sa | PROCESS AND INSTALLATION FOR PRODUCING MEDICAL QUALITY AIR |
US6013378A (en) * | 1997-03-17 | 2000-01-11 | Tenneco Packaging | HMW HDPE film with improved impact strength |
US5907942A (en) * | 1997-05-21 | 1999-06-01 | Tenneco Packaging | Stretch wrap films |
US6093480A (en) * | 1997-05-21 | 2000-07-25 | Tenneco Packaging | Stretch wrap films |
US5907943A (en) * | 1997-06-11 | 1999-06-01 | Tenneco Packaging Inc. | Stretch wrap films |
US5922441A (en) * | 1997-06-11 | 1999-07-13 | Tenneco Packaging Inc. | Stretch wrap films |
US6083611A (en) * | 1997-11-12 | 2000-07-04 | Tenneco Packaging, Inc. | Roll wrap film |
GB0425444D0 (en) † | 2004-11-18 | 2004-12-22 | Solvay | Multimodal composition for tapes, fibres and filaments |
EP2475520B1 (en) * | 2009-09-11 | 2018-10-24 | Tetra Laval Holdings & Finance S.A. | A barrier coated thermo-mechanically stable, heat sealable film, a packaging laminate comprising the film, a packaging container formed from the packaging laminate and a method for the production of the film |
CA2837591A1 (en) | 2013-12-19 | 2015-06-19 | Nova Chemicals Corporation | Polyethylene composition for extrusion coating |
JP6383479B1 (en) * | 2017-02-24 | 2018-08-29 | 旭化成株式会社 | Ethylene polymer and molded body |
CN112745556A (en) * | 2020-12-10 | 2021-05-04 | 金发科技股份有限公司 | High-haze PE blown film extinction composition and preparation method and application thereof |
CN113246569B (en) * | 2021-05-19 | 2023-06-06 | 上海紫江彩印包装有限公司 | Polyethylene label film and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63199242A (en) * | 1987-02-14 | 1988-08-17 | Showa Denko Kk | High-density polyethylene film and production thereof |
WO1988010281A1 (en) * | 1987-06-15 | 1988-12-29 | Neste Oy | Transparent, sterilisable package of plastic |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3231636A (en) * | 1958-03-20 | 1966-01-25 | Union Carbide Corp | High shear strength blends of high and low density polyethylene |
US3998914A (en) * | 1972-02-01 | 1976-12-21 | Du Pont Of Canada Limited | Film from a blend of high density polyethylene and a low density ethylene polymer |
FR2493854B1 (en) * | 1980-11-13 | 1985-10-11 | Naphtachimie Sa | IMPROVED POLYETHYLENE COMPOSITIONS FOR EXTRUSION IN PARTICULAR FOR EXTRUSION-BLOWING |
US4954391A (en) * | 1985-11-07 | 1990-09-04 | Showa Denko Kabushiki Kaisha | High density polyethylene type transparent film and process for production thereof |
-
1992
- 1992-03-27 EP EP92908842A patent/EP0582592A4/en not_active Withdrawn
- 1992-03-27 JP JP4508365A patent/JPH06506245A/en active Pending
- 1992-03-27 CA CA002107095A patent/CA2107095A1/en not_active Abandoned
- 1992-03-27 AU AU15734/92A patent/AU1573492A/en not_active Abandoned
- 1992-03-27 BR BR9205821A patent/BR9205821A/en not_active Application Discontinuation
- 1992-03-27 WO PCT/US1992/002557 patent/WO1992017539A1/en not_active Application Discontinuation
- 1992-03-30 ZA ZA922301A patent/ZA922301B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63199242A (en) * | 1987-02-14 | 1988-08-17 | Showa Denko Kk | High-density polyethylene film and production thereof |
WO1988010281A1 (en) * | 1987-06-15 | 1988-12-29 | Neste Oy | Transparent, sterilisable package of plastic |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 8839, Derwent World Patents Index; Class A17, AN 88-273997 * |
See also references of WO9217539A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1992017539A1 (en) | 1992-10-15 |
AU1573492A (en) | 1992-11-02 |
JPH06506245A (en) | 1994-07-14 |
ZA922301B (en) | 1993-08-23 |
EP0582592A1 (en) | 1994-02-16 |
BR9205821A (en) | 1994-08-23 |
CA2107095A1 (en) | 1992-09-30 |
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